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Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species toward Activation of Nitriles
- Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species toward Activation of Nitriles
- Noh, Hyeonju; Jeong, Donghyun; Ohta, Takehiro; Ogura, Takashi; Valentine, Joan Selverstone; Cho, Jaeheung
- DGIST Authors
- Jeong, Donghyun; Cho, Jaeheung
- Issue Date
- Journal of the American Chemical Society, 139(32), 10960-10963
- Article Type
- Activation Analysis; Ambient Conditions; Chemical Activation; Cobalt Compounds; Concerted Mechanism; Crystallography; Cyanides; Hammett Analysis; Isotope Labeling Experiments; Ligands; Overall Reactions; Peroxo Ligands; Spectroscopic Technique; Tetradentate Macrocyclic; X Ray Crystallography
- A mononuclear side-on peroxocobalt(III) complex with a tetradentate macrocyclic ligand, [CoIII(TBDAP)(O2)]+ (1), shows a novel and facile mode of dioxygenase-like reactivity with nitriles (R - C=N; R = Me, Et, and Ph) to produce the corresponding mononuclear hydroximatocobalt(III) complexes, [CoIII(TBDAP)(R - C(=NO)O)]+, in which the nitrile moiety is oxidized by two oxygen atoms of the peroxo group. The overall reaction proceeds in one-pot under ambient conditions (ca. 1 h, 40 °C). 18O-Labeling experiments confirm that both oxygen atoms are derived from the peroxo ligand. The structures of all products, hydroximatocobalt(III) complexes, were confirmed by X-ray crystallography and various spectroscopic techniques. Kinetic studies including the Hammett analysis and isotope labeling experiments suggest that the mechanistic mode of 1 for activation of nitriles occurs via a concerted mechanism. This novel reaction would be significantly valuable for expanding the chemistry for nitrile activation and utilization. © 2017 American Chemical Society.
- American Chemical Society
- Related Researcher
Biomimetic Materials Laboratory
Biomimetics; Metalloenzymes; Nitric Oxide Suppliers in Brain; Biomimetic Materials in Life
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- Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles
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